Patent GB-866335-A (GB)
Title: Process for the dyeing of fibres of polyacrylonitrile
Filed: 1957-07-25
Abstract: Dimethyl-benzyl-lauryl-ammonium chloride is prepared by the dropwise addition of benzyl chloride to continuously stirred N:N dimethyl laurylamine.  <FORM:0866335/IV (b)/1> where R = the alkyl radical corresponding to coconut fatty acid is prepared by the dropwise addition of benzyl chloride to continuously stirred N:N dimethyl-coconut fatty acid amine.  <FORM:0866335/IV (b)/2> is prepared by mixing proportionately 2-chloro-3-methylcymol and N:N dimethylaurylamine in ethanol and removing the latter under vacuum. The residue is stirred with ether and colourless crystals M.Pt. 95 DEG C. are obtained.  Dimethyl-benzyl-stearyl-ammonium chloride is prepared by adding benzyl chloride dropwise with stirring to a mixture of isopropanol and N:N dimethyl-stearylamine. Dihydroxyethylbenzyl-lauryl-ammonium chloride is prepared by adding dropwise and with stirring ethylene glycol and N:N dihydroxyethyl-laurylamine, excess benzyl chloride being removed under vacuum.  <FORM:0866335/IV (b)/3> is prepared by reaction of chloracetic acid octadecyl ester and N:N dimethyl cyclohexylamine and extracting any unreacted fractions with petroleum ether. <FORM:0866335/IV (b)/4> is prepared by stirring together lauryl bromide and N:N dimethylcyclohexylamine. Carbaminomethyl-dimethyl-3-(coconut fatty acid amido)-propyl-ammonium chloride is prepared by adding chloroacetamide to a mixture of N:N-(3-dimethylaminopropyl)-coconut fatty acid amide and methanol, the latter being subsequently removed under vacuum.  <FORM:0866335/IV (b)/5> is prepared by stirring together N:N, N1; N1 tetramethyl-ethylene diamine and lauryl bromide in anhydrous ether, decanting off the cooled liquid and drying the residue in vacuo.ALSO:Fibres of polyacrylonitrile or fibres containing acrylonitrile as a substantial component of a copolymer are dyed with basic dyestuffs free from sulphonic acid groups in the presence of a monoquaternary ammonium salt containing at least one aralkyl radical or at least one cycloalkyl radical or a grouping:- <FORM:0866335/IV(c)/1> <FORM:0866335/IV(c)/2> n which R indicates an aliphatic hydrocarbon radical with at least 8 and preferably 10-18 carbon atoms, R1 and R2 each a low molecular alkyl or hydroxy alkyl radical, R3 an aliphatic, cycloaliphatic or araliphatic radical which may be substituted, R4 a hydrogen atom or a low molecular alkyl or hydroxy alkyl radical, "Alkylene" a low molecular alkylene radical, m and n whole numbers of at most 2 and X an anion, with the stipulation that when m=1 the radical R3 stands for an aralkyl or cycloalkyl radical; in which R1 and R2 stand for alkyl radicals, if desired substituted or interrupted by hetero atoms, and "Alkylene" indicates an alkylene residue which may be substituted.  Preferably the quaternary ammonium salt contains an aliphatic hydrocarbon radical, especially an alkyl radical with 10-18 carbon atoms and also such salts as have unsubstituted hydrocarbon radicals attached to the quaternary nitrogen atom.  Alternative quaternary ammonium salts include <FORM:0866335/IV(c)/3> <FORM:0866335/IV(c)/4> in which R indicates a straight chain alkyl radical with 12-18 carbon atoms, R1 and R2 alkyl radicals with 1-2 carbon atoms, R3 a benzyl radical which can be substituted and Hal a halogen atom; <FORM:0866335/IV(c)/5> in which R is a straight-chain alkyl radical with 12-18 carbon atoms, R1, R2, R5 and R6 alky radicals with 1 or 2 carbon atoms, "Alkylene" an alkylene radical which may be substituted and Hal a halogen atom; and <FORM:0866335/IV(c)/6> in which R indicates a straight-chain alkyl radical with 11-17 carbon atoms, R1 and R2 alkyl radicals with 1 or 2 carbon atoms, R3 an alkyl radical which may be substituted by a reactive group and Hal a halogen atom. The fibres to be dyed may be produced from copolymers of polyacrylonitrile with acrylamide or acrylic esters.  Examples of basic dyestuffs free from sulphonic acid groups are dyes of the triarylmethane series which have in the p-position to the central carbon atom 1-3 amino, alkylamino aralkylamino or arylamino groups; oxazine dyes in which 2 carbon atoms of the oxazine ring are at the same time members of a 6-membered aromatic ring and having at least one amino group in the p-position with reference to the nitrogen atom of the oxazine ring; and polymethine dyes of formula: <FORM:0866335/IV(c)/7> in which R1 indicates an aromatic heterocyclic residue containing a basic group and X an anion.  The dyeing may be carried out by use of dye salts and quaternary ammonium salt in weakly acid aqueous baths at elevated temperature and atmospheric pressure.  Alternatively the dyeing may be carried out under superatmospheric pressure at 100 DEG -130 DEG C.  Examples are given.